CN113490737A

CN113490737A - Soap bars with improved flavor impact and active deposition

Info

Publication number: CN113490737A
Application number: CN202080017997.5A
Authority: CN
Inventors: A·M·阿加克赫德; P·钱达尔; C·沃尔什; N·库马; G·L·沙弗; 吴国卉
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2019-03-01
Filing date: 2020-02-24
Publication date: 2021-10-08
Also published as: EP3931295A1; US20220098528A1; MX2021010397A; ZA202105030B; BR112021014238A2; EP3931295B1; US11414632B2; WO2020178056A1

Abstract

The present invention relates to extruded bar compositions. More particularly, it relates to a soap bar composition that exhibits better fragrance release (fragrance impact) and better active deposition than conventional soap bars. This is achieved by ensuring that the amount of oleate soap is kept low while a certain amount of ricinoleate soap is added.

Description

Soap bars with improved flavor impact and active deposition

Technical Field

The present invention relates to extruded bar compositions. More particularly, it relates to a soap bar composition that exhibits better bloom and better active deposition than conventional soap bars.

Background

Surfactants have long been used in personal wash applications. There are many classes of products on the personal wash market, such as body washes, face washes, hand washes, soap bars, shampoos, and the like. Products sold as body washes, facial washes, and shampoos are typically in liquid form and are made from synthetic anionic surfactants. They are sold in plastic bottles/containers. Soap bars and hand sanitizer products typically contain soap. Soap bars do not need to be sold in plastic containers and are able to retain their own shape due to structuring in the form of a rigid solid. Soap bars are commonly sold in cartons made of paperboard.

Soap bars are typically prepared by one of two routes. One is called cast bar route (cast bar route) and the other is called milling and molding (plodded) route. The cast strand approach itself is very suitable for the preparation of low TFM (total fatty matter) strands. Total fatty matter is a common method of defining the quality of soap. It is defined as the total amount of fatty substances (mainly fatty acids) that can be separated from a sample of soap after decomposition with mineral acid (usually hydrochloric acid). In cast bar soap, the soap mixture is mixed with a polyol and poured into a casting, allowed to cool, and the bar is then removed from the casting. The cast strand approach enables production at relatively low production rates.

In the milling and plodding route, soap is prepared with a high water content, then spray dried to reduce the water content and cool the soap before adding the other ingredients, then the soap is extruded through a plodder and optionally cut and stamped to make the final soap bar. Milled and plodded bars typically have a high TFM of 60 to 80 wt%.

Milled and plodded bars are also known as extruded bars. They consist of a very large number of different types of soap. Most soaps contain both water insoluble soaps and water soluble soaps. Insoluble soaps are generally composed of a large number of higher chain C16 and C18 soaps (stearate and palmitate). They are typically included in soap bars to provide structuring benefits, namely: they provide shape to the soap. The soap bars also consist of water soluble soaps, which are typically unsaturated C18:1 and 18:2 sodium soaps (oleate soaps) in combination with short chain fatty acids (typically C8 to C12, even up to C14 soaps). Water soluble soaps are often used to assist in cleansing.

The inventors have found that when the amount of unsaturated higher chain fatty acid soap (e.g., oleate soap) is minimized or eliminated in the soap composition, higher fragrance impact and better delivery of actives onto the skin can be achieved. However, when such oleate soap is not contained, it is difficult to extrude such soap mass because of processing difficulties in the preparation step of molding (extrusion). The present inventors have been able to overcome this limitation by replacing the oleate moiety with an amount of sodium ricinoleate in combination with short chain fatty acid soaps (C8 to C12). The soap bar so prepared was found to have performance properties comparable to conventional soaps containing sodium oleate.

It was found that the newly formulated soap bar compositions showed significantly improved fragrance impact and enhanced active deposition compared to conventional soaps containing oleate.

Soap bars containing ricinoleate made using the extrusion route have been previously reported. CN103666884(Shanghai Bafang Fine Chemical,2014) discloses a sanguisorba antibacterial complex soap comprising the following raw materials in parts by weight: 0.05-0.15 part of garden burnet extract, 15-25 parts of sodium cocoate, 50-70 parts of sodium ricinoleate, 3-5 parts of cocamidopropyl amine oxide and 20 parts of water. Such bars contain very large amounts of ricinoleate soap and will have very high wear rates.

It is therefore an object of the present invention to provide a soap bar composition comprising low or no high molecular weight unsaturated soaps, such as oleate, thereby ensuring better fragrance impact and enhanced active delivery.

It is another object of the present invention to provide a soap bar composition which is low in oleate but can be easily processed in conventional molding presses to produce soap bars with acceptable in-use properties.

Disclosure of Invention

The present invention relates to a soap bar composition comprising soap in a total amount of 45 to 85 wt%, wherein the composition comprises:

a) from 1 to 40%, by weight of the composition, of a C8 to C12 fatty acid soap;

b) from 1 to 12%, by weight of the composition, ricinoleate soap;

wherein the composition comprises less than 8% oleate soap, by weight of the composition.

Detailed Description

These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the invention may be used in any other aspect of the invention. The word "comprising" is intended to mean "including", but not necessarily "consisting of …" or "consisting of …". In other words, the listed steps or options need not be exhaustive. It should be noted that the examples given in the following description are intended to illustrate the present invention, and are not intended to limit the present invention to these examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the working and comparative examples, or where otherwise explicitly indicated, all numbers in this description and in the claims indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Numerical ranges expressed as "x to y" are understood to include x and y. When multiple preferred ranges are described in the form of "x to y" for a particular feature, it is to be understood that all ranges combining the different endpoints are also contemplated.

The present invention relates to a soap bar composition. Soap bar composition refers to a cleansing composition comprising soap in its shaped solid form. The soap bar of the present invention comprises from 45 to 85% total soap. The term soap refers to salts of fatty acids. Preferably, the soap is a soap of a C8 to C24 fatty acid.

The cation may be an alkali metal, alkaline earth metal or ammonium ion, preferably an alkali metal. Preferably, the cation is selected from sodium or potassium, preferably sodium. The soap may be saturated or unsaturated. Saturated soaps are superior to unsaturated soaps in terms of stability. The oil or fatty acid may be of vegetable or animal origin.

Soaps can be obtained by saponification of oils, fats or fatty acids. The fats or oils commonly used to prepare soap bars may be selected from tallow, tallow stearin, palm oil, palm stearin, soybean oil, fish oil, rice bran oil, sunflower seed oil, coconut oil, babassu oil and palm kernel oil. The fatty acid may be derived from coconut, rice bran, groundnut, tallow, palm kernel, cotton seed or soybean.

Fatty acid soaps may also be synthetically prepared (e.g., by oxidation of petroleum or hydrogenation of carbon monoxide by the fischer-tropsch process). Resin acids, such as those present in tall oil, may also be used. Naphthenic acid may also be used.

The soap bar may additionally comprise synthetic surfactants selected from one or more of the classes of anionic, nonionic, cationic or zwitterionic surfactants, preferably from anionic surfactants. These synthetic surfactants according to the invention are comprised in less than 8%, preferably less than 4%, more preferably less than 1%, optimally absent from the composition.

The composition of the invention is in the form of a shaped solid, such as a bar. It is applied to a topical surface and left thereon for only a few seconds to a few minutes and then washed off with a large amount of water.

The soap bar of the present invention comprises from 45 to 85% total soap, preferably from 50 to 80%, more preferably from 55 to 78% soap by weight of the composition. The soap bars of the present invention comprise a substantial amount of low molecular weight soap (C8 to C12 soap), which is typically water soluble, which is from 1 to 40%, preferably from 2 to 35% by weight of the composition. It is preferred that the soap bar comprises from 35 to 65 wt% soap of C16 to C22 fatty acids, which are typically water insoluble soaps. A further preferred aspect relates to soap bars which are predominantly water insoluble, i.e. stearate and palmitate soaps, comprised at 40 to 72%, preferably 40 to 60% by weight of the composition.

The composition comprises from 1 to 12%, preferably from 4 to 10% by weight of the composition, ricinoleate soap. Ricinoleate soap is a salt of ricinoleic acid/12-hydroxyoleic acid.

Hydrolysis of castor oil yields about 85% ricinoleic acid. To ensure that the desired amount of ricinoleic acid soap is contained, the castor oil may be saponified by mixing with other oils in calculated amounts.

Importantly, according to the present invention, the composition comprises less than 8%, preferably less than 4%, more preferably less than 2%, further preferably less than 1% by weight of the composition of oleate soap. Optimally, oleate soap is not present in the composition. All soaps used in the preparation of the compositions of the present invention are preferably sodium soaps.

The soap bar composition typically comprises electrolyte and water. The electrolyte according to the present invention includes a compound that substantially decomposes into ions in water. The electrolyte according to the invention is not an ionic surfactant. Suitable electrolytes for inclusion in the soap making process are alkali metal salts. Preferred alkali metal salts include sodium sulfate, sodium chloride, sodium acetate, sodium citrate, potassium chloride, potassium sulfate, sodium carbonate and other mono-or di-or tri-salts of alkaline earth metals, more preferred electrolytes are sodium chloride, sodium sulfate, sodium citrate, potassium chloride, and particularly preferred electrolytes are sodium chloride, sodium sulfate, sodium citrate or combinations thereof. For the avoidance of doubt it is clear that the electrolyte is a non-soap material. The electrolyte is preferably contained at 0.4 to 6%, preferably 1 to 3%, by weight of the composition. Water is used as the pulping medium for the soap and is preferably included at 15 to 21% by weight of the composition.

The soap bar composition may be formed into bars by a process comprising extruding the mixture in a conventional die press. The molded mass may then optionally be cut to the desired size and imprinted with the desired indicia.

The various ingredients that make up the final bar composition are as follows:

organic and inorganic assistanceMaterial

The total amount of auxiliary materials used in the bar composition should be an amount of no more than 50%, preferably from 1 to 50%, more preferably from 3 to 45% by weight of the bar composition.

Suitable starch materials that may be used include native starches (from corn, wheat, rice, potato, tapioca, etc.), pregelatinized starches, various physically and chemically modified starches, and mixtures thereof. The term native starch refers to starch that has not been chemically or physically modified, also known as raw starch or native starch.

Preferred starches are native (native or native) starches from corn (maize, corn), tapioca, wheat, potato, rice and other natural sources thereof. Raw starches with different amylose to amylopectin ratios: such as corn (25% amylose); waxy corn (0%); high amylose corn (70%); potato (23%); rice (16%); sago (27%); cassava (18%); wheat (30%), etc. The raw starch may be used directly or modified during the preparation of the bar composition such that the starch becomes partially or fully gelatinized.

Another suitable starch is pregelatinized, which is a starch that has been gelatinized prior to addition as an ingredient in the bar composition of the invention. Various forms are available that will gel at different temperatures, such as cold water dispersible starches. A suitable commercial pregelatinized Starch is available from National Starch Co. (Brazil), under the trade name

CS 3400, but other commercially available materials with similar properties are suitable.

Polyhydric alcohols

Another organic adjuvant may be a polyol or a mixture of polyols. Polyol is a term used herein to designate a compound having a plurality of hydroxyl groups (at least two, preferably at least three) that is highly soluble, preferably readily soluble in water.

Many types of polyols are available, including: relatively low molecular weight short chain polyhydroxy compounds such as glycerol and propylene glycol; sugars such as sorbitol, mannitol, sucrose and glucose; modified carbohydrates, such as hydrolyzed starch, dextrins, and maltodextrins, and polymeric synthetic polyols, such as polyalkylene glycols, such as polyethylene glycol (PEG) and polypropylene glycol (PPG). Particularly preferred polyols are glycerol, sorbitol and mixtures thereof.

The amount of polyol may be important in forming a thermoplastic mass whose material properties are suitable for both high speed production (300 to 400 strands per minute) and for use as a personal wash bar. For example, when the polyol content is too low, the mass may not be sufficiently plastic at extrusion temperatures (e.g., 40 ℃ to 45 ℃), and the bars tend to exhibit higher gelatinization and wear rates. Conversely, when the polyol content is too high, the agglomerates may become too soft to form strands at high speeds at normal process temperatures.

In a preferred embodiment, the strip of the invention comprises from 0.1 to 20%, preferably from 0.5 to 15% by weight of a polyol. As noted above, preferred polyols include glycerol, sorbitol and mixtures thereof.

The auxiliary system may optionally include insoluble particles comprising one or more combinations of materials. Insoluble particles refer to materials that exist as solid particles and are suitable for personal washing. Preferably, mineral (e.g., inorganic) or organic particles are present.

The insoluble particles should not be perceived as being scraped (scratchy) or particulate and therefore should have a particle size of less than 300 microns, more preferably less than 100 microns, most preferably less than 50 microns.

Preferred inorganic particulate materials include talc and calcium carbonate. Talc is magnesium silicate mineral material having a layered silicate structure and Mg₃Si₄(OH)₂₂And can be obtained in hydrated form. It has a plate-like morphology and is substantially oleophilic/hydrophobic, i.e. it is wetted by oil rather than water.

Calcium carbonate or chalk exists in three crystalline forms: calcite, aragonite and vaterite. The natural morphology of calcite is rhombohedral or cubic, the natural morphology of aragonite is acicular or arborescent, and the natural morphology of vaterite is spherical.

Commercially, calcium carbonate or chalk, known as precipitated calcium carbonate, is produced by a carbonation process in which carbon dioxide gas is bubbled through an aqueous suspension of calcium hydroxide. In this process, the crystal type of calcium carbonate is calcite or a mixture of calcite and aragonite.

Examples of other optional insoluble inorganic particulate materials include aluminosilicates, aluminates, silicates, phosphates, insoluble sulfates, borates, and clays (e.g., kaolin, china clay), and combinations thereof.

Organic particulate materials include insoluble polysaccharides such as highly cross-linked or insoluble starches (e.g., by reaction with a hydrophobe such as octyl succinate) and cellulose; synthetic polymers such as various polymer latexes and suspension polymers; insoluble soaps and mixtures thereof.

The bar composition preferably comprises from 0.1 to 25% by weight of the bar composition, preferably from 5 to 15% by weight of these mineral or organic particles.

Sunscreens may optionally be present in the personal care composition. When opacifiers are present, the cleansing bar is typically opaque. Examples of opacifiers include titanium dioxide, zinc oxide, and the like. A particularly preferred opacifier that may be used when an opaque soap composition is desired is ethylene glycol mono or distearate, for example in the form of a 20% solution in sodium lauryl ether sulfate. An alternative opacifier is zinc stearate.

The product may take the form of a water-clear, i.e. transparent soap, which in this case does not contain an opacifier.

Preferred soap bars of the invention have a pH of from 8 to 11, more preferably from 9 to 11.

Preferred bars may additionally comprise up to 30 wt% benefit agent. Preferred benefit agents include moisturizers, emollients, sunscreens and anti-aging compounds. The reagents are added at appropriate steps during the process of making the strip. Some benefit agents may be introduced as macroscopic domains (macro domains).

Other optional ingredients such as antioxidants, perfumes, polymers, chelating agents, colorants, deodorants, dyes, emollients, moisturizers, enzymes, foam boosters, bactericides, additional antimicrobials, lathering agents, pearlescent agents, skin conditioning agents, stabilizers, superfatting agents, sunscreens may be added in suitable amounts in the method of the present invention. Preferably, the ingredients are added after the saponification step. Preferably, sodium metabisulphite, ethylenediaminetetraacetic acid (EDTA), borax or ethylene hydroxy diphosphonic acid (EHDP) is added to the formulation.

According to another aspect of the present invention there is provided the use of a composition for providing enhanced flavour impact or enhanced deposition of actives.

The invention will now be illustrated by the following non-limiting examples.

Examples

Example A, B and 1, 2: fragrance impact of the inventive compositions compared to control samples

The following two bar compositions as shown in table 1 were prepared:

the bar prepared above was tested for its fragrance impact using the following method:

the fragrance availability of the cleaning compositions of the present invention is assessed by three consumer-related parameters:

dry smell-when the consumer perceives the smell of the strip.

Duration of use-fragrance from 8% soap solution indicates the release of fragrance during use.

After use-fragrance intensity-measurement after washing off

Sample preparation:

dry smell

The bar was smelled by the consumer to evaluate the fragrance of the soap to quantify the intensity of the fragrance emitted by the composition. To evaluate and quantify dry odor, fragrance in the headspace of the soap bar was measured by headspace gas chromatography and the components were identified by mass spectrometry. To this end, the samples were prepared by milling the soap bars with a cheese grinder to obtain fine particles. 1 gram of the composition was placed in a 20ml vial, immediately sealed with a rubber septum and equilibrated at 27 ℃ for 2.5 hours to achieve equilibration of headspace volatiles. Subsequently, the vial was placed in an autosampler at 30 ℃.

During use

The consumer evaluates the soap during use according to the amount of fragrance. To investigate this, an 8% solution was prepared by dissolving 4g of milled soap in 46g of DM water in a sealed bottle at 50 ℃. 3ml of the above soap solution was placed in a 20ml vial and sealed with a rubber septum. The vials were equilibrated at 27 ℃ for 2.5 hours and sampled similarly to dry sniff samples. Subsequently, the vial was placed in an autosampler at 30 ℃.

After use

To quantify the deposition of benefit agents on the skin surface. An 8% soap solution was prepared according to the procedure described above. Human SKIN sample (VITRO-SKIN)^TMIMS corp, a synthetic substrate intended to simulate the surface chemistry of human skin) were subjected to in vitro performance tests. Mixing the obtained 4cm × 4cm VITRO-SKIN^TMImmersed in the soap solution for 15 seconds and then rinsed by shaking it in 25ml of water for 30 seconds. This procedure was repeated 3 times with 25ml of fresh DM water each time. Then, the VITRO-SKIN is added^TMPlaced in a vial, immediately sealed with a rubber septum and equilibrated at 27 ℃ for 2.5 hours to achieve equilibration of headspace volatiles. Subsequently, the vial was placed in an autosampler at 30 ℃.

Headspace analysis

The samples were analyzed by Gas Chromatography (GC) analysis of headspace gas. In this process, the instrument used was a Solid Phase Microextraction (SPME) system using a Hewlett packard G1530A (GC) Flame Ionization Detector (FID). The Mass Spectrometer (MS) used was a Hewlett Packard 5973 mass selective detector. This instrument measures the relative abundance of fragrance compounds in the headspace on the fragrance/fragrance-emitter/water mixture and on the fragrance/water mixture. A 1 gram fragrance/fragrance releaser/water mixture was prepared in a 20ml GC headspace sample vial sealed with a lid with septum (from Gerstel, Inc) and maintained at 27 ℃. The GC column was a DB-1 column from Agilent J & W (internal diameter 0.25mm, length 10m, stationary phase thickness 0.25 μm). The GC conditions were as follows:

splitless-less mode sample injector with helium as carrier gas. The sample inlet was heated to 265 ℃ and a purge gas flow at zero minutes flowed to the split vent at 100 ml/min. The column was in constant flow mode with a flow rate of 0.7 ml/min. Oven temperature rise: held at 500 ℃ for 2 minutes, then the oven temperature was increased at a rate of 35 ℃/minute to 100 ℃, 15 ℃/minute to 200 ℃ and then 3 ℃/minute.

The MS conditions were as follows:

solvent delay 1 minute, scan from low mass 35 to high mass 300.

The conditions of the autosampler are as follows:

incubate at 30 ℃ for 30 minutes. SPME fiber was inserted into the sample headspace for 10 minutes, then injected into the injector and desorbed at 265 ℃ for 1 minute.

Vials from the three samples were analyzed using capillary GC columns. PDMS (i.e., polydimethylsiloxane; nonpolar phase) and PEG (i.e., polyethylene glycol; polar phase) columns are used for this purpose.

The output from the GC is recorded as a series of peaks, each peak representing one compound in the mixture passing through the detector. For data comparison, peak areas of the peaks were obtained and added up to show perfume levels. The area of the peak is proportional to the amount of compound present. The area can be approximated by treating the peaks as triangles. The area of the triangle is calculated by multiplying the peak height by its full width at half maximum.

Table 2 shows the average total area of the peaks obtained by the three different samples described above.

The areas are then normalized with respect to the respective samples being compared. The values of the samples according to the invention (examples 1 and 2) are the area ratio of the respective sample to the control sample (examples a and B), respectively.

TABLE 2

Study of	Example A	Example 1	example-B	Example 2
					Dry smell	1.00	1.05	1.00	1.17
During use	1.00	3.89	1.00	4.10
					After use (deposition)	1.00	2.76	1.00	1.95

The data in table 2 below show that the samples according to the invention (examples 1 and 2) have a greater effect on the perception of fragrance than the respective control samples.

Examples C, D and 3: the composition of the invention (example 3) is contrasted with certain commercially available soaps (examples C and D) Influence of fragrance

Soap compositions shown in table 3 below were prepared.

TABLE 3

The samples were tested for dry and in-use smells (aroma release) and the results are summarized in table 4 below:

TABLE 4

Study of	Example C	Example D	Example 3
				Dry smell (soap, without water)	1.00	1.42	1.42
Application period (soap solution-fragrance releasing)	1.00	1.28	4.7

The data in table 4 above show that the composition of the invention (example 3) gives a better release of fragrance (impact of fragrance during use) compared to compositions outside the invention (examples C and D).

Claims

1. A soap bar composition comprising from 45 to 85% by weight total soap, wherein the composition comprises:

a) from 1 to 40%, by weight of the composition, of a C8 to C12 fatty acid soap;

b) from 1 to 12%, by weight of the composition, ricinoleate soap;

2. The composition of claim 1, wherein the composition comprises less than 4%, preferably less than 2%, more preferably less than 1%, by weight of the composition, of oleate soap.

3. The composition of claim 2 wherein oleate soap is absent from the composition.

4. A composition according to any preceding claim, wherein all soaps in the composition are sodium soaps.

5. A composition according to any preceding claim, wherein the total amount of stearate and palmitate soaps is from 40 to 72% by weight of the composition.

6. Use of a composition according to any of the preceding claims for providing an enhanced flavour impact.

7. Use of a composition according to any preceding claim to provide enhanced deposition of actives.